EP0353724A1 - Wärmeentwickelbares photoempfindliches Material - Google Patents

Wärmeentwickelbares photoempfindliches Material Download PDF

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Publication number
EP0353724A1
EP0353724A1 EP89114225A EP89114225A EP0353724A1 EP 0353724 A1 EP0353724 A1 EP 0353724A1 EP 89114225 A EP89114225 A EP 89114225A EP 89114225 A EP89114225 A EP 89114225A EP 0353724 A1 EP0353724 A1 EP 0353724A1
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EP
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Prior art keywords
group
photosensitive material
heat developable
developable photosensitive
substituted
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EP89114225A
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French (fr)
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EP0353724B1 (de
Inventor
Tetsuro Kojima
Tomoyuki Koide
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers

Definitions

  • This invention relates to a heat developable photosensitive material and, more particularly, to a heat developable photosensitive material which is excel­lent in S/N ratio (the maximum image density to the minimum density) and has high sensitivity.
  • Heat developable photosensitive materials which utilize silver halides as a photosensitive component are well-known in the field of this art, and described, e.g., in Shashin Kogaku no Kiso (which means funda­mentals of photographic engineering), volume “Higinen Shashin” (which means “Nonsilver Photography"), pages 242 to 255, Corona Co. (1982); Eizo Jouho (which means image information), page 40 (Apr. 1978); Nebletts, Handbook of Photography and Reprography , 7th Ed., pages 32 to 33, Van Norstrand Reinhold Company; U.S.
  • either dye image, negative or positive to original ones can be obtained by changing dye-providing compounds and/or silver halides to be used in kind (as disclosed in U.S. Patents 4,463,079, 4,474,867, 4,478,927, 4,507,380, 4,500,626 and 4,483,914, JP-A-58-149046 (the term "JP-A” as used herein means an "unexamined published Japanese patent application"), JP-A-58-149047, JP-A-59-152440, JP-A-59-154445, JP-A-59-165054, JP-A-59-180548, JP-A-59-­168439, JP-A-59-174832, JP-A-59-174833, JP-A-59-174834, JP-A-59-174835, JP-A-62-65038, JP-A-61-23245, EP-A-­210660, EP-A-220746,
  • the above-described heat developable photosensitive materials are development-processed under heating to high temperatures, so they have generated fog (or lowering of Dmax in photosensitive materials of the kind which make a positive response to a positive original) to a considerable extent, in contrast to ordinary photosensitive materials to undergo devel­opment-processing in the vicinity of room temperature. That is, They have been hard to provide photographs excellent in image distinguishability (with high S/N).
  • antifoggant-containing heat developable photosensitive materials disclosed in JP-A-59-168442, JP-A-59-111636, JP-A-59-177559, JP-A-60-168545, JP-A-60-180199, JP-A-60-­180563, JP-A-61-53633, JP-A-62-78554, JP-A-62-123456, JP-A-63-133144, and so on.
  • an object of this invention is to provide a heat developable photosensitive material which is excellent in image distinguishability (S/N ratio), as well as sensitivity.
  • a heat developable photosensitive material of this invention has at least one photosensitive silver halide emulsion layer on a support, and contains at least one compound selected from those represented by the following general formulae (I) and (II): wherein R represents an alkylene group, an alkenylene group, an aralkylene group or an arylene group, which each may be substituted; Y represents R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each represents a hydrogen atom, or a substituted or unsubstituted alkyl, aryl, alkenyl or aralkyl group; X represents R′ represents a hydrogen atom, or a substituted or unsubstituted or alkenyl group; R ⁇ represents a hydrogen atom, or a substitutive group therefor; M represents a hydrogen atom, an alkali metal ion, an ammonium group, or a group capable of being cleaved
  • R represents a straight-chain or branched alkylene group (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), a straight-chain or branched alkenylene group (e.g., vinylene, 1-methylvinylene), a straight-chain or branched aralkylene group (e.g., benzylidene), or an arylene group (e.g., phenylene, naphthylene). These groups each may have a substituent, such as an alkoxy group, a halogen atom or so on.
  • alkylene group e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene
  • alkenylene group e.g., vinylene, 1-methylvinylene
  • a straight-chain or branched aralkylene group e.g., benzylidene
  • an arylene group e.g
  • R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each represents a hydrogen atom, a substituted or unsub­stituted alkyl group (e.g., methyl, ethyl, propyl, 2-­dimethylaminoethyl), a substituted or unsubstituted aryl group (e.g., phenyl, 2-methylphenyl), a substituted or unsubstituted alkenyl group (e.g., propenyl, 1-­methylvinyl), or a substituted or unsubstituted aralkyl group (e.g., benzyl, phenetyl).
  • a substituted or unsub­stituted alkyl group e.g., methyl, ethyl, propyl, 2-­dimethylaminoethyl
  • a substituted or unsubstituted aryl group e.g., phen
  • R′ represents a hydrogen atom, or a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, 2-dimethylaminoethyl, 2-imidazolylethyl, 2-­dimethylaminopropyl), substituted or unsubstituted alkenyl group (e.g., propenyl, 1-methylvinyl).
  • alkyl group e.g., methyl, ethyl, propyl, 2-dimethylaminoethyl, 2-imidazolylethyl, 2-­dimethylaminopropyl
  • substituted or unsubstituted alkenyl group e.g., propenyl, 1-methylvinyl
  • R ⁇ represents a hydrogen atom, or a group by which hydrogen atom can be replaced, with specific examples including a halogen atom (e.g., fluorine, chlorine, bromine), a substituted or unsubstituted alkyl group containing 1 to 6 carbon atoms (e.g., methyl, trifluoromethyl, ethyl, n-butyl), a substituted or unsubstituted aryl group containing 6 to 12 carbon atoms (e.g., phenyl, 4-methylphenyl), a substituted or unsubstituted alkoxy group containing 1 to 6 carbon atoms (e.g., methoxy, ethoxy), a substituted or unsubstituted aryloxy group containing 6 to 12 carbon atoms (e.g., phenoxy, 4-methylphenoxy), a sulfonyl group containing 1 to 12 carbon atoms (e.g., methanesulfony
  • M represents a hydrogen atom, an alkali metal ion (e.g., sodium, potassium), an ammonium group (e.g., trimethylammonium chloride, dimethylbenzylammonium chloride), or a group capable of being converted to H or an alkali metal under an alkaline condition (e.g., acetyl, cyanoethyl, methanesulfonylethyl).
  • an alkali metal ion e.g., sodium, potassium
  • an ammonium group e.g., trimethylammonium chloride, dimethylbenzylammonium chloride
  • a group capable of being converted to H or an alkali metal under an alkaline condition e.g., acetyl, cyanoethyl, methanesulfonylethyl.
  • Z represents a substituted or unsubstituted amino group (including the salt form thereof, e.g., amino group, hydrochloride of amino group, methylamino group, dimethylamino group, hydrochloride of dimethyl­amino group, dibutylamino group, dipropylamino group, N-­dimethylaminoethyl-N-methylamino group), a substituted or unsubstituted quaternary ammoniumyl group (e.g., trimethylammoniumyl chloride, dimethylbenzylammoniumyl chloride), a substituted or unsubstituted sulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, p-toluene­sulfonyl), a substituted or unsubstituted carbamoyl group (e.g., unsubstituted carbamoyl, methylcar
  • Each group represented by Z may further be substituted by an arbitrary combination of R and Z.
  • R should be a substituted or unsubstituted alkylene
  • Y should be all of R2, R3, R5, R6 and R7 should be a hydrogen atom
  • X should be -S- or -O-
  • R ⁇ should be a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
  • M should be a hydrogen atom, a sodium ion, a potassium ion or an ammonium group
  • n, m and l each should be 1
  • Z should be a substituted or unsubstituted amino group or a salt thereof, an alkylthio group substituted by an amino group, or a nitrogen-containing heterocyclic group.
  • R should be a substituted or unsubstituted alkylene group
  • Y′ should be R14 and R15 should be both a hydrogen atom
  • X′ should be -S- or -O-
  • M should be a hydrogen atom, a sodium ion, a potassium ion or an ammonium group
  • n should be 1
  • Z should be a substituted or unsubstituted amino group, a salt thereof, an alkylthio group, or a heterocyclic group.
  • the compounds represented by the general formula (I) is preferable to those represented by the general formula (II).
  • the compounds of this invention represented by the general formula (I) can be synthesized with ease according to the methods described in Organic Synthesis, IV, 569 (1963), Journal of the American Chemical Society, 45 , 2390 (1923), Chemische Berichte, 9 , 465 (1876), and JP-A-61-99121.
  • the compounds of this invention represented by the general formula (II) can be synthesized by reference to the methods described in Advances in Heterocyclic Chemistry, volume 9, pages 165 to 209 (1968), Journal of Pharmaceutical Society Japan, volume 71, pages 1481 to 1484 (1951), U.S. Patent 2,823,208, and JP-A-61-156646.
  • These compounds may be incorporated in any constituent layer of a heat developable photosensitive material. However, it is desirable that they should be incorporated in a photosensitive layer or an adjacent layer thereto (e.g., an interlayer, a protective layer), especially a photosensitive layer.
  • a photosensitive layer or an adjacent layer thereto e.g., an interlayer, a protective layer
  • the above-described compounds can be added to a photographic emulsion in any step of the emulsion-making, or at any stage between the conclusion of the emulsion-making and right before the coating. However, it is generally preferred to add them at any stage between the conclusion of the emulsion-­making and right before the coating.
  • the heat developable photosensitive material of this invention basically has, on a support, a photosensitive silver halide and a binder, and therein can optionally be contained an organic metal salt oxidizing agent, dye-providing compounds (a reducing agent can function as the compound, in such cases as described hereinafter), and so on.
  • ingredients are incorporated in the same layer in many cases, they may be incorporated into separate layers so long as the layers are situated so as to permit reactions among the ingredients.
  • the drop in sensitivity can be prevented by incorporating a colored dye-providing compound into a layer disposed under a silver halide emulsion layer.
  • a reducing agent though preferably incorporated in a heat developable photosensitive element, may be externally supplied to the photosensitive element, e.g., through the diffusion from a dye-fixing element as described hereinafter.
  • At least three silver halide emulsion layers having their individual sensitivities in different spectral regions are used in combination.
  • a combi­nation of a blue-sensitive, a green-sensitive and a red-­sensitive layers a combination of a green-sensitive, a red-sensitive and an infrared-sensitive layers, and so on.
  • These layers can be arranged in various orders known in connection with color photographic materials of general type. Each of these sensitive layers may be divided into two or more layers, if needed.
  • auxiliary layers such as a protective layer, a subbing layer, an interlayer, a yellow filter layer, an antihalation layer, a backing layer and so on can be provided.
  • Silver halides which can be used in this invention may include any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
  • the silver halide emulsion to be used in this invention may be that of a surface latent image type or that of an internal latent image type.
  • the emulsion of an internal latent image type is used as direct reversal emulsion on combined use with a nucleating agent or an optical fogging means.
  • a so-called core/shell emulsion in which the interior and the surface of the grains constitute different phases respectively may be used.
  • the silver halide emulsion may be monodisperse or polydisperse one, and a mixture of different mono­disperse emulsions may be used.
  • a preferred grain size of the silver halide used in this invention ranges from 0.1 to 2 ⁇ m, particularly from 0.2 to 1.5 ⁇ m.
  • a crystal habit of the silver halide grains used in this invention may be any of those of a cube, an octahedron, a tetradecahedron, a tablet having a high aspect ratio, and so on.
  • any of the silver halide emulsions described in U.S. Patent 4,500,626 (column 50), U.S. Patent 4,628,021, RD-17029 (1978), JP-A-62-253159, and so on can be used in this invention.
  • Those silver halide emulsions though may be used in the primitive condition, are usually chemically sensitized.
  • sulfur sensitization, reduction sensitization, noble metal sensitization and other processes known in emulsions for ordinary photosensitive materials can be used independently or in combination.
  • These chemical sensitization processes can be performed in the presence of a nitrogen-containing heterocyclic compound (as disclosed in JP-A-62-253159).
  • a coverage of the photosensitive silver halide used in this invention ranges from 1 mg/m2 to 10 g/m2 based on the silver.
  • organic metal salts can be used as oxidizing agent together with photosensitive silver halides.
  • organic metal salts organic silver salts are particularly preferred as such an oxidizing agent.
  • silver salts of carboxylic acid having an alkynyl group such as silver phenylpropiolate disclosed in JP-A-60-113235, and acetylene silver disclosed in JP-­A-61-249044 are also useful.
  • Organic silver salts as described above may be used in combination of two or more thereof.
  • the organic silver salt can be used in an amount of 0.01 to 10 moles, preferably 0.01 to 1 mole, per mole of the photosensitive silver halide. It is appropriate that a coverage of the photosensitive silver halide and that of the organic silver salt should amount to from 50 mg/m2 to 10 g/m2 in all, based on the silver.
  • Conventional antifoggants or photographic stabi­lizers can also be used together in this invention. Suitable examples of such agents, mention may be made of the azoles and the azaindenes described in RD-17643, pages 24 to 25 (1978), the nitrogen-containing carboxyl­ic acids and phosphoric acids disclosed in JP-A-59-­168443, the mercapto compounds and the metal salts thereof disclosed in JP-A-59-111636, the acetylene compounds disclosed in JP-A-62-87957, and so on.
  • the silver halides to be used in this invention may be spectrally sensitized with methine dyes or the like.
  • Dyes usable for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine yes, styryl dyes and hemioxonol dyes.
  • sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used in particular for the purpose of supersensiti­zation.
  • Such sensitizing dyes may be added to emulsions during, before or after the chemical ripening step, or may be added thereto before or after the nucleation of silver halide grains according to U.S. Patents 4,183,756 and 4,225,666.
  • the amount added generally ranges from about 10 ⁇ 8 to 10 ⁇ 2 mole per mole of the silver halide.
  • Binders which can be preferably used in constituent layers of the photosensitive material and the dye fixing material are hydrophilic ones.
  • hydrophilic binders mention may be made of those described in JP-A-62-253159, pages 26 to 28. More specifically, transparent or translucent hydrophilic binders, e.g., natural compounds such as proteins including gelation and gelatin derivatives, cellulose derivatives, and polysaccharides including starch, gum arabic, dextran, pullulan and the like; and synthetic high molecular compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymers and so on, can be preferably used.
  • highly water-­absorbing polymers disclosed in JP-A-62-245260 that is, a homopolymer of a vinyl monomer containing -COOM or -SO3M (where M represents a hydrogen atom or an alkali metal), copolymers prepared from vinyl monomers of the above-described kind alone, or copolymers prepared from the above-described vinyl monomer(s) and other vinyl monomers (e.g., sodium methacrylate, ammonium meth­acrylate, Sumika Gel L-5H, produced by Sumitomo Chemical Co., Ltd.) can be used. These binders can be used as a combination of two or more thereof.
  • the used of the above-­described highly water-absorbing polymers enables the rapid absorption of water. Further, the use of the highly water-absorbing polymers in a dye fixing layer or the protective layer thereof can prevent the dyes transferred into the dye fixing material from retrans­ferring into others.
  • a coverage of the binder used in this invention is properly controlled to not more than 20 g/m2, preferably not more than 10 g/m2, and particularly preferably not more than 7 g/m2.
  • Constituent layers of the photosensitive material and the dye fixing material can contain various kinds of polymer latexes for the purpose of enhancing physical properties as film, such as dimensional stability, anticurling, adhesion resistance, cracking resistance and prevention of pressure sensitization or desensitization.
  • any of the polymer latexes disclosed in JP-A-62-­245258, JP-A-62-136648, JP-A-62-110066, and so on can be used.
  • polymer latexes having a low glass transition point (below 40°C) can prevent the generation of cracking when used in the mordanting layer, and those having a high glass transition point can produce an anticurl effect when used in the backing layer.
  • Reducing agents which can be used in this invention include those known in the field of heat developable photosensitive materials. Also, dye-­providing compounds having reducing power described hereinafter are included therein. (When the dye-­providing compounds of such as kind are employed, other reducing agents can also be used together.) In addition, precursors of reducing agents, which themselves do not have any reducing powder, but acquire it through the interaction with a nucleophilic agent or heat in the course of development, can be used.
  • an electron transmitter and/or a precursor thereof can optionally be used in combination therewith in order to accelerate the transfer of an electron between the nondiffusible reducing agent and a developable silver halide.
  • Such an electron transmitter or a precursor thereof can be chosen from the above-described reducing agents and precursors thereof. It is desirable that the electron transmitter or the precursor thereof should have mobility greater than that of the nondiffusible reducing agent (electron donator) to be used together. Particularly useful electron transmitters are 1-phenyl-­3-pyrazolidones or aminophenoles.
  • a nondiffusible reducing agent (electron donator) to be used in combination with such an electron transmitter described above may be any of the above-­described reducing agents so long as it does not move, in a substantial sense, from one constituent layer to another in the photosensitive material.
  • electron donator an electron donator
  • hydroquinones sulfonamidophenols, sulfonamidonaphthols, the compounds disclosed as electron donators in JP-A-53-110827, nondiffusible dye-providing compounds having a reducing powder as described hereafter, and so on.
  • a preferred amount of a reducing agent used in this invention ranges from 0.01 to 20 moles, particularly from 0.1 to 10 moles, per 1 mole of the silver.
  • silver can be used as an image forming substance, and compounds capable of producing or releasing mobile dyes in correspondence or counter-correspondence to the reduction of silver ion to silver under a high temperature condition, that is to say, dye-providing compounds can also be contained together with the silver.
  • Couplers compounds capable of forming dyes by the oxidative coupling reaction
  • These couplers may be four-equivalent or two-equivalent ones.
  • two-equivalent couplers containing a nondiffusible group as their individual splitting-off groups and producing a diffusible dye by the oxidative coupling reaction can be preferably used.
  • Such a nondiffusible group may assume the form of polymer chain.
  • dye-providing compounds examples include compounds which have such a function as to release or diffuse imagewise a diffusible dye.
  • the compounds of this type can be represented by the following general formula (LI): (Dye - Y) n - Z (LI) wherein Dye represents a dye moiety, a dye moiety whose absorption band is temporarily shifted to shorter wave lengths, or a precursor of a dye moiety; Y represents a mere bonding hand, or a linkage group; Z represents such a group as to cause an imagewise change in diffusibility of the compound of the formula (Dye-Y) n -Z, or to release imagewise the moiety Dye to bring about a difference in diffusibility between the released Dye and (Dye-Y) n -Z in correspondence or counter-correspondence with the photosensitive silver salt imagewise bearing with an latent image; and n represents 1 or 2, and when n is 2, two (Dye-Y)'s may be the same or
  • dye-providing compounds represented by the general formula (LI) mention may be made of those classified into the following groups from (1) to (5). Making additional remarks, the compounds classified into the groups from (1) to (3) are those of the kind which form diffusible dye images in counter-­correspondence with the development of silver halide (positive dye images), while the compounds classified into the groups (4) and (5) are those of the kind which form diffusible dye images in correspondence with the development of silver halide (negative dye images).
  • the group (1) consists of dye developing agents in which a hydroquinone type developing agent and a dye component are connected to each other, with specific examples including those disclosed in U.S. Patents 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972, and so on.
  • dye developing agents are diffusible under an alkaline condition, but rendered nondiffusible by the reaction with silver halide.
  • the group (2) consists of nondiffusible com­pounds of the kind which can release a diffusible dye under an alkaline condition, but lose that ability upon the reaction with silver halide, as disclosed in U.S. Patent 4,503,137.
  • Specific examples of each compounds as described above include the compounds capable of releasing a diffusible dye by the intramolecular nucleophilic substitution reaction as disclosed in U.S. Patent 3,980,479 and so on, and the compounds capable of releasing a diffusible dye by the intramolecular rearrangement reaction of an isooxazolone ring as disclosed in U.S. Patent 4,199,354, and so on.
  • the group (3) consists of nondiffusible compounds of the kind which can release a diffusible dye by the reaction with a reducing agent which has remained unoxidized through development, as disclosed in U.S. Patent 4,559,290, EP-A-220746, Kokai Giho 87-6199, and so on.
  • Specific examples of such compounds include those disclosed in U.S. Patents 4,139,389 and 4,139,379, JP-A-59-185333, JP-A-57-84453 and so on, which can release a diffusible dye by the intramolecular nucleophilic substitution reaction after they are reduced; those disclosed in U.S.
  • More preferred examples of compounds belonging to this group include those having both a N-X bond (where X represents an oxygen, sulfur or nitrogen atom) and an electron attractive group in a molecule, as disclosed in EP-A-220746, Kokai Giho 87-6199, Japanese Patent Application Nos. 62-34953 and 62-34594 (corresponding to JP-A-63-201653 and JP-A-63-201654, respectively), and so on; those having both a SO2-X bond (where X has the same meaning as described above) and an electron attractive group in a molecule, as disclosed in Japanese Patent Application No.
  • those having both a N-X bond and an electron attractive group in a molecule are preferred in particular.
  • Specific examples of such compounds include those cited in EP-A-220746 as the compound examples (1) to (3), (7) to (10), (12), (13), (15), (23) to (26), (31), (32), (35), (36), (40), (41), (44), (53) to (59), (64) and (70), and those cited in Kokai Giho 87-6199 as the compound examples (11) to (23).
  • the group (4) consists of couplers of the kind which have a diffusible dye residue as a splitting-off group and release the diffusible dye by the reaction with the oxidation product of a reducing agent (DDR couplers).
  • DDR couplers include those disclosed in British Patent 1,330,524, JP-B-48-­39165 (the term "JP-B” as used herein means an "examined Japanese patent publication"), U.S. Patents 3,443,940, 4,474,867 and 4,483,914, and so on.
  • the group (5) consists of compounds of the kind which can reduce silver halides or organic silver salts, and release a diffusible dye upon the reduction of these silver salts (DRR compounds). Since these compounds to not require the combined use with other reducing agents, they have an advantage in that they can produce images free from stains arising from the oxidative decomposition products of reducing agents. Representatives of these DRR compounds are disclosed in U.S. Patents 3,928,312, 4,053,312, 4,055,428 and 4,336,322, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819, JP-A-51-104343, RD-17465, U.S.
  • DRR compounds which can be preferably used in this invention, mention may be made of the compounds illustrated on the columns from 22nd to 44th of the above-cited U.S. Patent 4,500,626, particularly those illustrated as the compound examples (1) to (3), (10) to (13), (16) to (19), (28) to (30), (33) to (35), (38) to (40), and (42) to (64).
  • the compounds disclosed on the columns from 37th to 39th of the above-­cited U.S. Patent 4,639,408 are useful, too.
  • dye-providing compounds other than the above-­described couplers and the compounds represented by the general formula (LI) dye silver compounds in which an organic silver salt and a dye are bound to each other (as described in Research Disclosure , Vol. 169, pages 54 to 58 (May 1978)), azo dyes which can be used in heat developable silver dye bleach process (as disclosed in U.S. Patent 4,235,957, Research Disclosure , Vol. 144, pages 30 to 32 (Apr. 1976)), leuco dyes (as disclosed in U.S. Patents 3,985,565 and 4,022,617), and so on can be employed in this invention.
  • Hydrophobic additives including dye-providing compounds, nondiffusible reducing agents and so on can be introduced into constituent layers of the photosensitive material according to known methods described, e.g., in U.S. Patent 2,322,027.
  • high boiling organic solvents as disclosed in JP-A-59-­83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-59-178454, JP-A-59-178455, JP-A-59-178457 and so on can be used, if necessary, together with low boiling organic solvents having a boiling point ranging from 50°C to 160°C.
  • An amount of the high boiling organic solvent used is controlled to 10 g or less, preferably 5 g or less, per 1 g or the dye-providing compounds.
  • the amount of the high boiling organic solvent used per 1 g of the binder it is appropriately 1 ml or less, preferably 0.5 ml of less, and particularly preferably 0.3 ml or less.
  • hydrophobic additives into the photosensitive material can be effected in accordance with a dispersion method utilizing polymers as disclosed in JP-B-51-39853 and JP-A-51-59943.
  • surfactants In dispersing hydrophobic compounds into a hydrophilic colloid, various kinds of surfactants can be used. For instance, those exemplified as surfactant on the pages 37 and 38 of JP-A-59-157636 can be employed therein.
  • a dye-fixing material is used in combination with the photosensitive material.
  • the dye-­fixing material and the photosensitive material may be provided independently on separate supports, or may be provided in layers on the same support.
  • the correlation of the dye-fixing material with the photosensitive material and as for the relations of the dye-fixing material to a support and to a white reflective layer, those described on the column 57 of U.S. Patent 4,500,626, can be applied to this invention.
  • a dye-fixing material which is preferably used in this invention has at least one layer containing a mordant and a binder.
  • mordants known in the photographic art can be used, and specific examples thereof include those described on the columns 58 and 59 of U.S. Patent 4,500,626, on the pages from 32 to 41 of JP-A-61-88256, and particularly preferably include those disclosed in JP-A-62-244043 and JP-A-62-244036.
  • dye-accepting high molecular compounds as disclosed in U.S. Patent 4,463,079 may be used as the mordant.
  • the dye-fixing material can be provided with auxiliary layers, such as a protective layer, a peeling-­apart layer, an anticurl layer and so on, if desired.
  • auxiliary layers such as a protective layer, a peeling-­apart layer, an anticurl layer and so on, if desired.
  • a protective layer such as a peeling-­apart layer, an anticurl layer and so on.
  • a plasticizer for enhancing a facility in peeling apart the dye-fixing material from the photosensitive material.
  • a plasticizer for enhancing a facility in peeling apart the dye-fixing material from the photosensitive material.
  • a slipping agent for enhancing a facility in peeling apart the dye-fixing material from the photosensitive material.
  • Specific examples thereof include those disclosed in JP-A-62-253159 (page 25), JP-A-62-245253 and so on.
  • various silicone oils (covering from dimethylsilicone oil to modified silicone oils prepared by introducing various kinds of organic groups into dimethylsiloxane) can be further used.
  • effective silicone oils mention may be made of a wide variety of modified silicone oils described in "Hensei Silicone Oil” Gijutsu Shiryo P6-18B (which means technical data on modified silicone oils), published by Shin-etsu Silicone Co., Ltd.
  • carboxy-modified silicone (trade name; X-22-3710) is used to advantage.
  • silicone oils disclosed in JP-A-62-­215953 and Japanese Patent Application No. 62-23687 are effective, too.
  • the photosensitive materials and the dye-fixing material may contain a discoloration inhibitor.
  • Suitable discoloration inhibitors include, e.g., antioxidants, ultraviolet absorbents and certain metal complexes.
  • Suitable antioxidants include, e.g., chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine compounds, and spiroindane compounds. Also, the compounds disclosed in JP-A-61-159644 are effective as antioxidants.
  • Suitable ultraviolet absorbents include benzo­triazole compounds (as disclosed in U.S. Patent 3,533,794), 4-thiazolidone compounds (as disclosed in U.S. Patent 3,352,681), benzophenone compounds (as disclosed in JP-A-46-2784), and other compounds as disclosed in JP-A-54-48535, JP-A-62-136641 and JP-A-61-­88256.
  • the ultraviolet absorbing polymers disclosed in JP-A-62-260152 are also effective.
  • Suitable metal complexes include the compounds disclosed, e.g., in U.S. Patents 4,241,155, 4,245,018 (columns 3 to 36) and 4,254,195 (columns 3 to 8), JP-A-­62-174741, JP-A-61-88256 (pages 27 to 29), Japanese Patent Application Nos. 62-234103 and 62-31096 (corresponding to JP-A-1-75568 and JP-A-63-199248), and so on.
  • Discoloration inhibitors for preventing the dyes transferred in the dye-fixing material from undergoing discoloration may be incorporated in advance in the dye-­fixing material, or supplied externally (e.g. from the photosensitive material) to the dye-fixing material.
  • antioxidants ultraviolet absorbents and metal complexes may be used in combi­nation.
  • a brightening agent may be used in the photosensitive material and the dye-­fixing material.
  • a brightening agent should be incorporated in the dye-fixing material or supplied externally (e.g., from the photosensitive material) thereto.
  • a brightening agent which can be used, mention may be made of the compounds as described in K. Veenkataraman (editor), The Chemistry of Synthetic Dyes , volume V, chapter 8, JP-A-61-143752, and so on. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline com­pounds, carbostyryl compounds and the like can be effectively used as the brightening agent.
  • These brightening agents can be used in combination with discoloration inhibitors.
  • Hardeners suitable for the use in constituent layers of the photosensitive material and the dye-fixing material are those disclosed in U.S. Patent 4,678,739 (column 41), JP-A-59-116655, JP-A-62-245261, JP-A-61-­18942, and so on.
  • aldehyde type hardeners e.g., formaldehyde
  • aziridine type hardeners epoxy type hardeners
  • vinylsulfon type hardeners e.g., N,N′-ethylene-bis(vinylsulfonylacet­amido)ethane
  • N-methylol type hardeners e.g., dimethylol urea
  • high molecular hardeners e.g., the compounds disclosed in JP-A-62-234157.
  • various surfac­ tants can be used in constituent layers of the photo­sensitive materials and the dye-fixing material.
  • surfactants suitable for the above-­described purposes include those disclosed in JP-A-62-­173463, JP-A-62-183457, and so on.
  • organic fluorinated compounds may be incorporated in constituent layers of the photosensitive material and the dye-fixing material.
  • fluorine-containing surfactants disclosed in JP-B-57-­9053 (columns 8 to 17), JP-A-61-20944, JP-A-62-135826 and so on, and hydrophobic fluorine compounds including oily fluorine compounds, such as fluorine-containing oil, and solid fluorine-containing resins, such as tetrafluorinated ethylene resin.
  • a matting agent can be used in the photo­sensitive material and the dye-fixing material.
  • a matting agent which can be used mention may be made of silicon dioxide, the compounds described in JP-A-61-88256 (page 29), such as polyolefins, polymethylmethacrylate and the like, and the substances disclosed in Japanese Patent Application Nos. 62-110064 and 62-110065 (corresponding to JP-A-63-274944 and JP-A-­ 63-274952, respectively), such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like.
  • thermal solvents defoaming agents, antibacteria and antimolds, colloidal silica and so on may be incorporated in constituent layers of the photosensitive material and the dye-fixing material.
  • specific examples of these additives are described, e.g., in JP-A-61-88256 (pages 26 to 32).
  • image-formation accelerators can be used.
  • the image-formation accel­erators have such functions that they can accelerate the redox reaction between a silver salt oxidizing agent and a reducing agent, the production of dyes, the decomposition of dyes or the release of diffusible dyes from dye-providing substances, and the transfer of the dyes from the photosensitive material to the dye-fixing material.
  • the image-formation accelerators are classified into groups, such as bases, base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, compounds having an interaction with silver or silver ion, and so on. In general, substances belonging to these groups have combined functions, and each substance usually has some of the above-cited acceleration effects. Details of these accelerators and their functions are described in U.S. Patent 4,678,739 (pages 38 to 40).
  • base precursors there can be given the salts prepared from bases and organic acids to be decarboxylated by heating, and compounds capable of releasing amines by undergoing the intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. More specifically, such compounds are described in U.S. Patent 4,511,493, JP-A-­62-65038, and so on.
  • Various development stoppers can be used in the photosensitive material and/or the dye-fixing material of this invention for the purpose of stationarily producing images of the same quality in spite of fluctuations in processing temperature and processing time during the development.
  • development stopper as used herein describes a compound of the kind which can stop the development by rapidly neutralizing a base or reacting with a base after the proper development to lower the base concentration in the film, or can retard the development through the interaction with silver or a silver salt.
  • Specific examples thereof include acid precursors capable of releasing acids by heating, electrophilic compounds capable of causing a substi­tution reaction with a base present together by heating, nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof, and so on. Details of these compounds are described in JP-A-62-253159 (pages 31 to 32).
  • paper and synthetic polymers films
  • usable supports include films of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide and celluloses (e.g., triacetyl cellulose), those prepared by dispersing a pigment, such as titanium oxide, into such films as cited above, film process synthetic paper made from polypropylene or the like, paper made from a mixture of synthetic resin pulp, such as polyethylene pulp, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metals, cloths, glasses, and so on.
  • These materials may be used individually as they are, or some of them are used in a condition that they are laminated with a synthetic polymer, such as polyethylene or the like, on one side or both sides thereof.
  • a synthetic polymer such as polyethylene or the like
  • a hydrophilic binder On the surface of a support as described above, a hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, and an antistatic agent such as carbon black may be coated.
  • exposing methods e.g., a method of directly taking photographs of sceneries and figures with a camera or the like, a method of exposing the photosensitive material to light through a reversal film or a negative film using a printer, an enlarger or the like, a method of scanning rays of light passing through a slit over an original with an exposure apparatus installed in a copying machine or the like, a method of forcing a light emission diode or a wide variety of laser devices to emit light by sending thereto electric signals bearing with image information, and irradiating the photosensitive material with the emitted light, a method of putting out image information on an image display unit such as a CRT, a liquid crystal display, an electroluminescence display or a plasma display screen, and exposing the photosensitive material to the displayed image directly or through an optical system, and so on.
  • image display unit such as a CRT, a liquid crystal display, an electroluminescence display or a plasma display screen
  • Light sources suitable for recording images in the photosensitive material include natural light, a tungsten lamp, light emission diodes, laser light sources, CRT light sources and so on, as described in U.S. Patent 4,500,626 (column 56).
  • imagewise exposure can be performed by using a wavelength changing element made by combining a nonlinear optical material and a coherent light source such as laser beams.
  • nonlinear optical material refers to the material of the kind which can create a nonlinearity relationship between the electric field and the polarization to emerge upon application of a strong photoelectric field such as laser beams.
  • Nonlinear optical material examples include inorganic compounds represented by lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, BaB2O4 and the like, urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), and the compounds as disclosed in JP-A-61-53462 and JP-A-62-210432.
  • KDP potassium dihydrogen phosphate
  • POM 3-methyl-4-nitropyridine-N-oxide
  • the form of the wavelength changing element that of a single-crystal light-waveguide lane, that of a fiber and so on are known, and each is useful in this invention.
  • image information those obtained from video cameras, electronic still cameras or the like, television signals of NTSC color system (NTSC: National Television System Committee), image signals obtained by dividing an original into a great number of image elements using a scanner or the like, and image signals produced by the use of a computer which are represented by CG and CAD can be utilized.
  • NTSC National Television System Committee
  • the photosensitive material and/or the dye-­fixing material may be provided with a conductive heat-­emission layer to function as heating means for heat development or diffusion transfer of dyes.
  • a conductive heat-­emission layer to function as heating means for heat development or diffusion transfer of dyes.
  • transparent or opaque heat-emission elements described, e.g., in JP-A-61-145544 can be utilized.
  • Making an additional remark, such as conductive layer as described above can function as an antistatic layer, too.
  • the dye diffusion transfer step may be carried out at the same time as the heat development step, or after the conclusion of the heat development step. In the latter case, it is possible to achieve the transfer as far as heating temperature adopted in the transfer step is in the range of the temperature adopted in the heat development step to room temperature. However, the transfer can be accomplished more efficiently under a heating tempera­ture ranging from 50°C to the temperature lower than that adopted in the heat development step by about 10°C.
  • the transfer of dyes may be caused by heat alone, may be carried out with the aid of a solvent of the kind which can promote the dye transfer.
  • a method of heating in the presence of a small amount of solvent (especially water) to achieve the development and the transfer simultaneously or successively can be used to advantage.
  • a preferred heating temperature is in the range of 50°C to a boiling point of the solvent used. For instance, temperatures from 50°C to 100°C are desirable when water is used as the solvent.
  • bases those given as examples of image-formation accelerators hereinbefore can be used.
  • a low boiling solvent, or a mixture of a low boiling solvent with water or a basic aqueous solution can be used for the above-described purpose(s).
  • surfactants, antifoggants, slightly soluble metal salts and complexing compounds may be contained in solvents as described above.
  • solvents each can be used in such a manner that it may be given to either the dye-fixing material or the photosensitive material, or both of them.
  • Each solvent can serve its purpose when used in such a small amount as to be below the weight of the solvent having a volume equivalent to the maximal swelling volume of the whole layers coated (especially below the weight obtained by deducting the weight of the whole layers coated from the weight of the solvent having a volume equivalent to the maximal swelling volume of the whole layers coated).
  • the solvent can be given to the photosensitive material or the dye-fixing material in accordance with, e.g., the method described in JP-A-61-147244 (page 26). Also, it can be used in such a condition as to be incorporated in advance in the photosensitive material or the dye-fixing material in the microencapsulated from or the like.
  • a hydrophilic thermal solvent which melts at high temperatures though it is a solid at ordinary temperatures, into the photosensitive material or the dye-fixing material.
  • the hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material, or both of them. It may be incorporated in any of the constituent layers including emulsion layers, interlayers, protective layers and dye-fixing layers. However, it is desirable that the hydrophilic thermal solvent should be incorporated into a dye-fixing layer and/or the layers adjacent thereto.
  • hydrophilic thermal sol­vents include ureas, pyrimidines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds.
  • a high boiling solvent may be incorpo­rated in the photosensitive material and/or the dye-­fixing material in order to promote the dye transfer.
  • the heating in the development and/or the transfer step can be effected, e.g., by the direct contact with the heated block and plate, or the contact with a hot plate, a hot presser, a hot roller, a halogen lamp heater or an infrared and far infrared lamp heater, or the passage through high temperature atmosphere.
  • any of conventional heat developing apparatuses can be employed.
  • apparatuses as disclosed in JP-A-59-75247, JP-A-59-­177547, JP-A-59-181353, JP-A-60-18951, JP-A-U-62-25944 (the term "JP-A-U” as used herein means an "unexamined published Japanese utility model application"), and so on can be preferably used.
  • the solution (I), the solution (II) and the solution (III) described below were simultaneously added over a 30-minute period at the same and constant flow rate to an aqueous gelatin solution (containing 20 g of gelatin, 1 g of potassium bromide and 0.5 g of HO(CH2)2S(CH2)2OH in 800 ml of water, and kept at 50°C) with thoroughly stirring.
  • a dye-adsorbed mono­disperse pebble-like silver bromide emulsion having an average grain size of 0.42 ⁇ m was prepared.
  • the solution (I) and the solution (II) described below were simultaneously added over a 60-minute period at the same and constant flow rate to an aqueous solution (containing 20 mg of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the agent A illustrated below in 730 ml of water, and kept at 60.0°C) with thoroughly stirring.
  • the solution (III) (containing the sensitizing dye illus­trated below in methanol) was further added.
  • a dye-adsorbed monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 ⁇ m was prepared.
  • the solution (I) and the solution (II) described below were simultaneously added over a 30-minute period at the same and constant flow rate to an aqueous gelatin solution (containing 20 g of gelatin, 3 g of potassium bromide and 0.3 g of HO(CH2)2S(CH2)2S(CH2)2OH in 800 ml of water, and kept at 60°C) with thoroughly stirring. Then, the solution (III) and the solution (IV) described below were further added simultaneously over a 20-minute period at the same and constant flow rate. After the conclusion of the addition, 30 ml of a 1% water solution of potassium iodide was furthermore added. Subse­quently, the dye solution described below was added.
  • the above-­described composition was added to 40 ml of cyclo­ hexanone, and heated up to about 60°C to be converted into a homogeneous solution.
  • This solution was mixed with 100 g of a 10% water solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 ml of water with stirring, and dispersed thereinto over a period of 10 minutes using a homogenizer rotating at 10,000 r.p.m.
  • the thus obtained dispersion was called a gelatin dispersion of dye-providing compound.
  • a heat developable photosensitive material (1) having the multilayer structure described in Table 1 and capable of making a posi-posi response was produced using the emulsions and the dispersions prepared in the above-described manners.
  • Aerosol OT produced by American Cyanamid
  • Aerosol OT produced by American Cyanamid
  • Benzoguanamine resin average particle size: 10 ⁇ m
  • Photosensitive materials (2) and (3) each was prepared in the same manner as the photosensitive material (1), except that a conventional antifoggant shown in Table 3 was incorporated into the first, the third and the fifth layers. Further, photo­sensitive materials (4) to (15) (in accordance with this invention) were prepared in the same manner as the comparative samples, except that the compounds of this invention were incorporated instead of the conventional antifoggants, respectively. An amount of the anti­foggant used in each layer was 2.5x10 ⁇ 3 mole per mole of silver halide.
  • Each of the color photosensitive materials having the above-described multilayer structure was exposed to light emitted from a tungsten lamp through B, G, R and Gray color separation filters with continuously altered densities for 1/10 second under an illuminance of 4,000 lux.
  • the superposed materials were heated for 15 seconds with heating rollers whose temperature was controlled so that a temperature of the water-absorbed film might go up to 85°C.
  • the photosensitive material was peel apart from the dye-fixing material. Thereupon, blue, green, red and gray images were obtained in the dye-fixing material in correspondence to the B, G, R and Gray color separation filters.
  • the photosensitive materials of this invention were excellent in Dmax and Dmin, as well as sensitivity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP89114225A 1988-08-05 1989-08-01 Wärmeentwickelbares photoempfindliches Material Expired - Lifetime EP0353724B1 (de)

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EP0559101A1 (de) * 1992-03-02 1993-09-08 Canon Kabushiki Kaisha Lichtempfindliches, wärmeentwickelbares Material und Bildherstellungsverfahren unter Anwendung desselben
EP1422551A1 (de) * 2002-11-14 2004-05-26 Agfa-Gevaert Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind
EP1598207A1 (de) * 2004-05-17 2005-11-23 Agfa-Gevaert Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind
US7097961B2 (en) 2004-05-17 2006-08-29 Agfa Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials

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JPH05127334A (ja) * 1991-10-31 1993-05-25 Fuji Photo Film Co Ltd 熱現像カラー感光材料
US6511187B1 (en) 1992-02-20 2003-01-28 Kopin Corporation Method of fabricating a matrix display system
DE4214196C2 (de) * 1992-04-30 2003-08-28 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
US5300420A (en) * 1993-06-01 1994-04-05 Minnesota Mining And Manufacturing Company Stabilizers for photothermography with nitrile blocking groups
US5298390A (en) * 1993-06-07 1994-03-29 Minnesota Mining And Manufacturing Company Speed enhancers and stabilizers for photothermography
US5541054B1 (en) † 1995-04-20 1998-11-17 Imation Corp Spectral sensitizing dyes for photothermographic elements

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EP0559101A1 (de) * 1992-03-02 1993-09-08 Canon Kabushiki Kaisha Lichtempfindliches, wärmeentwickelbares Material und Bildherstellungsverfahren unter Anwendung desselben
US5529889A (en) * 1992-03-02 1996-06-25 Canon Kabushiki Kaisha Heat developable photosensitive material and image forming method which uses the same
EP1422551A1 (de) * 2002-11-14 2004-05-26 Agfa-Gevaert Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind
EP1598207A1 (de) * 2004-05-17 2005-11-23 Agfa-Gevaert Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind
US7097961B2 (en) 2004-05-17 2006-08-29 Agfa Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials

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US5082763A (en) 1992-01-21
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JPH0244336A (ja) 1990-02-14
DE68923410D1 (de) 1995-08-17
JPH07119951B2 (ja) 1995-12-20

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